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pubs.acs.org/EF

Conversion of Anisole Catalyzed by Platinum Supported on

Alumina: The Reaction Network
Ron C. Runnebaum,† Rodrigo J. Lobo-Lapidus,†,§ Tarit Nimmanwudipong,† David E. Block,†,‡ and
Bruce C. Gates*,†
†
Department of Chemical Engineering and Materials Science, University of California, One Shields Avenue, Davis, California 95616,
United States
‡
Department of Viticulture and Enology, University of California, One Shields Avenue, Davis, California 95616, United States

bS Supporting Information
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ABSTRACT: The conversion of anisole (a compound representative of bio-oils) in the presence of H2 was investigated with a flow
reactor operated at a temperature of 573 K and a pressure of 140 kPa with a platinum on alumina catalyst. Analysis by gas
chromatography mass spectrometry led to the identification of more than 40 reaction products, the most abundant being phenol,
2-methylphenol, benzene, and 2,6-dimethylphenol. The kinetically significant reaction classes were transalkylation, hydrodeoxy-
genation, and hydrogenation. Selectivity-conversion data were used to determine an approximate quantitative reaction network
accounting for phenol, 2-methylphenol, 2-methylanisole, and 4-methylphenol as primary products. Pseudo-first-order rate constants
for the formation of these products are 12, 2.8, 0.14, and 0.039 L/(g of catalyst  h), respectively. A more complete qualitative
network was inferred on the basis of the observed products and the assumption that the reaction classes leading to the most
abundant primary products were responsible for the minor and trace products. The removal of oxygen was evidenced by the
production of benzene.

’ INTRODUCTION prospect of having similar value for biomass conversion. Because

Catalytic conversion of feedstocks formed by pyrolysis of
cellulosic and lignin-rich biomass is an attractive option for the
production of renewable liquid transportation fuels.1 3 Although
conversion data characterizing complex bio-oil feedstocks have
been reported,4 23 there is a lack of fundamental understanding
of the classes of reactions involved. Sharma et al.6 10 and Vitolo
et al.11 investigated the catalytic conversion of various bio-oils,
with catalysts such as the zeolite HZSM-5. Adjaye et al.12 14
focused on the conversion of fast pyrolysis bio-oils catalyzed by
zeolites and silica aluminas. A few researchers have investigated
the catalytic hydrotreatment of bio-oils,15 23 demonstrating
significant removal of oxygen. The complexity of the feedstocks,
however, limits the usefulness of these data for predicting
the conversions of other feedstocks. In these investigations, the
individual products found in the conversion of bio-oils have
sometimes been grouped into classes (lumps), and approximate
reaction networks showing conversion to the lumps have been
reported.
The conversion of individual, prototypical bio-oil compounds
has also been investigated by a number of researchers. The
catalytic reaction networks presented by these researchers, which
were determined from conversions measured in the absence of
H2, are limited either to primary products (or occasionally
primary and secondary products) or to products that have been
lumped into classes of similar compounds (e.g., phenol, alkyl-
phenol, and alkylated ether lumps).24 35
Investigations of the reactions of individual compounds have
been of value in advancing the understanding of petroleum
and coal-liquid hydroprocessing reactions,36 and they offer the
today’s instruments allow analysis of products in much more
detail than was reported in early work defining the reactions of
petroleum and coal refining, it is possible to determine reaction
networks that are much more detailed than those reported in
these early investigations. Our goal was to determine such a
detailed reaction network for a compound representative of
lignin-derived bio-oils and an important functional group
characterizing compounds in them; consequently, we chose
a compound, anisole, that is aromatic and incorporates an
ether linkage.
The catalytic hydrotreating of anisole was investigated by
Bredenberg et al.37 and by Hurff and Klein,38 who used sulfided
hydrotreating catalysts; reaction networks, however, were either
not reported or limited to few products. Adjaye and Bakhshi,12,14,34
Hurff and Klein,38 Samolada et al.,17 Sharma and Bakhshi,6 10 and
Elliott et al.15 reported mass balance closures, but others have not.
The following paper is part of a series39 42 concerned with
various bio-oil compounds; early results for anisole have been
communicated.39 We now report details, which include mass
balances, selectivity-conversion plots with error bounds, rate
constants of product formation, and a quantitative reaction net-
work, characterizing the conversion of anisole catalyzed by a
supported metal, Pt/Al2O3, in the presence of H2. We also report
the design of a reactor system that includes the capability for
extensive online analysis of gas products by gas chromatography
Received: July 21, 2011
Revised: August 25, 2011
Published: August 28, 2011

r 2011 American Chemical Society 4776 dx.doi.org/10.1021/ef2010699 | Energy Fuels 2011, 25, 4776–4785
Energy & Fuels
Figure 1. Schematic representation of once-through, packed-bed flow reactor system. Abbreviations: TC, thermocouple; PI, pressure indicator; PT,
pressure transducer; PG, analogue pressure gauge; BPR, back-pressure regulator; MFM, mass flow meter; MFC, mass flow controller.
and at-line analysis of liquid products by gas chromatography
with identification of products by gas chromatography/mass
spectrometry; we have used this system to evaluate reaction
products and establish the reaction network.
’ EXPERIMENTAL METHODS
Materials. Anisole (methoxybenzene, 99.8%) was purchased from
Sigma-Aldrich. Pt/γ-Al2O3 powder (<100 mesh) containing 1 wt % Pt
was acquired from Sigma-Aldrich. N2 (99.997%, from Praxair), further
purified by passage through a BHT-4 hydrocarbon trap (Agilent
Technologies) to remove traces of hydrocarbon, was used as an inert
carrier gas in the gas solid reaction system and in the gas chromato-
graphs. H2 (99.999%), generated from deionized water by electrolysis in
a model 40H gas generator (Domnick Hunter), was used as a reactant in
the catalytic conversion experiments and in the gas chromatographs.
Helium (99.995%, Praxair) was purified by passage through a BHT-4
trap (Agilent Technologies) to remove traces of hydrocarbon, a BMT-4
trap (Agilent Technologies) to remove moisture, and a BOT-4 trap
(Agilent Technologies) to remove oxygen prior to use in the gas
chromatographs. Zero-air (<0.1 ppm hydrocarbon (as methane)) was
generated from house air in a model UHP-10ZAW zero air generator
(Domnick Hunter) and was used in the gas chromatograph flame
ionization detectors. The BET surface area of the catalyst was measured
with a Micromeritics ASAP 2020 instrument, and the dispersion of the
platinum in the catalyst was measured with a Micromeritics Autochem II
Chemisorption Analyzer.
Flow Reactor System. Catalytic reaction experiments were carried
out with a once-through packed-bed flow reactor (316 L stainless steel,
O.D. = 0.5 in., wall thickness = 0.035 in.). A schematic diagram of the
flow system is shown in Figure 1.
The liquid reactant was preloaded at room temperature into a syringe
pump (Model 500D, Teledyne-ISCO), which was used as a liquid feed
reservoir. Mass flow controllers (Model SLA5850S, Brooks Instruments)
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were used to measure and control gas flow rates. N2 was used as the
carrier gas. H2, when used as a reactant, was mixed into the carrier gas
stream via a Swagelok union cross (4-way) downstream of the mass flow
controllers. The gas stream was mixed with vaporized anisole reactant at
the inlet of the reactor in the top zone of a three-zone furnace. At the top
of the downflow reactor, a Swagelok union cross provided three inlets to
the reactor, one for gases, one for liquid fed through a capillary tube
(stainless steel, O.D. = 1/16 in., I.D. = 0.020 in., Model U-104, Upchurch
Scientific), and one for a thermocouple (Model HKMTSS-040U-12,
Omega Engineering), which was placed near the tip of the capillary tube
to measure the temperature of vaporization of the liquid feed. From
the outlet of the reactor, the product stream flowed through a Swagelok
(3-way) union tee, which also allowed mounting of a thermocouple
(Model KQSS-116U-18, Omega Engineering) inside the reactor im-
mediately downstream of the packed bed.
The reactor was mounted in a three-zone furnace (Series 3210,
Applied Test Systems), which was designed for precise temperature
control. Five thermocouples were used to measure temperatures inside
(at the two locations mentioned above) and outside the reactor. The
temperatures of the vaporization zone and packed bed were controlled
by using the measurements of temperature determined with thermo-
couples in the reactor. Thermocouple wells extending axially into each zone
of the furnace enabled positioning of thermocouples near the outer wall
of the reactor and monitoring of temperatures in each zone at the outer
reactor wall. The temperature of the zone downstream of the packed bed
was controlled by using the signal of the thermocouple mounted at the
outside wall of the reactor. The temperatures of the three heating zones
were controlled separately.
The packed bed, holding 4.1 401.5 mg of catalyst particles, was
typically 10 to 30 mm long. Glass wool and the packed bed of catalyst
particles were positioned at the midpoint of the reactor and furnace. To
provide nearly flat radial velocity and temperature profiles in the bed, the
catalyst particles were mixed with particles of inert α-Al2O3 (A634-3
alundum, Fisher, 90 mesh particle size).
dx.doi.org/10.1021/ef2010699 |Energy Fuels 2011, 25, 4776–4785
Energy & Fuels
After exiting the reactor, the product stream flowed through stainless
steel tubing that was heated by electrical heating tape (HTC-120,
Omega), extending from the exit of the reactor to the inlet of a
condenser. Water at approximately 10 °C was used as a coolant, and
the outlet gas stream exited the condenser at approximately 12 °C,
as measured by a thermocouple (KQMSS-020G-6, Omega). Liquid
samples were collected at intervals of approximately 20 min from the
bottom of the condenser and weighed. The flow rate of the gas product
stream was monitored with a SLA 7860S mass flow meter (Brooks
Instruments).
Safety features enabled redundant monitoring of key control points.
For instance, both pressure transducers (PTI-S-NG250-22AQ, Swagelok)
and analogue pressure gauges (PGI-63B-PG200-LAQX-J, Swagelok)
were placed upstream of the reactor and downstream of the condenser;
the pressure in the system was controlled by a manual back-pressure
regulator (44-2300 Series, Tescom). Reactor temperatures were mea-
sured in each zone, both inside and outside of the reactor; upper limits
were included in the control program for automatic shut-off of power to
the furnace.
Product Analysis. Analysis of the products in the liquid samples was
performed with an Agilent 7890A gas chromatograph (GC) equipped
with a 5975C mass selective detector (MSD) incorporating a quadru-
pole mass analyzer. Analyte separation was achieved with a DB-624
Agilent J&W column (0.25 mm/60 m/1.4 μm) with 2.4 mL/min helium
carrier gas flow rate and a temperature ramp program. Peaks were
identified by using the Agilent quality match factor (Qual), which is based
on how well the ion ratios match those of the NIST EI mass spectral
library database standard; each compound except water and methanol
scored greater than 90. Retention times of some of the compounds were
confirmed by use of calibration samples. Product quantification was
carried out with an Agilent 7890A GC using a flame ionization detector
(FID); analyte separation was achieved with a DB-624 Agilent J&W
column (0.25 mm/60 m/1.4 μm). The operating parameters of the GC-
FID were developed to obtain essentially the same peak retention times
and separations as with the GC-MSD. The FID was operated at 300 mL/
min zero-air and 25 mL/min H2 flow rates. Calibration curves, each with
at least five points, were used to quantify the following products:
benzene, cyclohexanone, phenol, 2-methylanisole, 4-methylanisole,
2-methylphenol, 4-methylphenol, and 2,6-dimethylphenol. Other pro-
ducts were analyzed semiquantitatively on the basis of results obtained
for chemically similar components (containing the same numbers of
carbon and oxygen atoms).
A GC (Agilent 7890A), equipped with three sample loops, five
columns, and three detectors (one FID and two TC detectors), was
used to analyze the gas effluent from the condenser. Each of the sample
loops was 500 μL in volume. Hydrocarbons were separated in an HP-Al/
S (19095P-S25, 50 m long/0.53 mm in I.D./15 μm in film thickness)
Agilent J&W capillary column with a helium carrier gas flow rate of
27 mL/min, and the components were quantified by analysis with an
FID. The FID was operated at 300 mL/min zero-air and 25 mL/min H2
flow rates. Fixed gases and methane were separated with three Agilent
1/8-in stainless-steel packed columns mounted in series: HayeSep Q (6 ft),
HayeSep N (8 ft), and Molsieve 13X (10 ft), and the components were
quantified with a TCD with helium carrier gas at a pressure of 70 kPa. H2
was separated in a 4-ft Molsieve 13X packed column and quantified with
a TCD using N2 carrier gas. Temperature and carrier gas flow ramps
were used to improve the retention time and separation of compounds.
Gas samples were taken online at approximately 30 min intervals; each of
the sample loops was actuated, nearly simultaneously, to load the flow
paths to each of the detectors and to characterize the gas stream. Peak
identification was carried out by comparison with a NIST traceable
Agilent Technologies/Praxair RGA gas calibration standard (5184-
3545, Lot No. 091509R). Single-point calibrations, determined using
data collected with compounds (listed in the Supporting Information,
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SI Table 1) in the gas calibration standard, were used to quantify
products in the gas stream.
Catalyst Loading, Preparation, and Testing. The Pt/Al2O3
catalyst was held in place in the reactor with approximately 0.1 g of
quartz wool mounted near the axial center of the reactor. A bed of
approximately 2 g of α-Al2O3 was placed on the quartz wool; down-
stream of it was a bed of catalyst particles mixed with 1 2 g of α-Al2O3,
and upstream of that was another bed of 2 g of α-Al2O3 particles. The
catalyst was heated in N2 flowing at 70 mL/min at NTP and H2 (flowing
at a rate of 30 mL/min at NTP) at a rate of 5 °C/min to 573 K and held
at this temperature for 30 min prior to the start of reactant flow. The
catalyst mass was in the range of 4.1 401.5 mg.
The catalytic conversion of anisole was carried out at 573 K and
approximately 140 kPa; the anisole flow rate was 0.03 mL/min, and the
N2 and H2 flow rates were 70 and 30 mL(NTP)/min, respectively. The
range of the weight hourly space velocity (WHSV) was 17.6 437 (g of
anisole)/(g of catalyst  h), varied by changing the catalyst mass. Fresh
catalyst was used for each experiment. Experiments were typically run for
6 h time-on-stream.
Data Analysis. Conversions of anisole were determined on the
basis of mass balance calculations for the reaction system. The terms in
the mass balance included the flow rate of anisole into the reactor and
the flow rates of the liquid condensate and gas streams out of the
condenser; the mass of the packed bed was measured before and after
each experiment to allow a determination of the accumulation of mass in
it. The mass of reactant entering the reactor was calculated from the
volumetric flow rate and density of the reactant (flowing at approxi-
mately NTP). The mass of liquid condensate was determined periodi-
cally by measuring the mass of liquid collected in each vial and summing
over the samples. The mass of the reactant leaving the condenser in the
gas phase was calculated from the flow rate of the gas and by using an
Antoine vapor pressure correlation and assuming that the inert gas was
saturated with the reactant at the exit temperature of the condenser.
Because the condenser did not drain perfectly, the mass of liquid
remaining in the condenser at the end of each experiment was
determined from the mass of liquid fed into the system prior to the
collection of liquid at the bottom of the condenser.
Conversions (X) were calculated as the molar flow rates of anisole
reactant consumed divided by the total molar flow rate of anisole fed.
The mass of products, taken to be the mass of reactant consumed, was
determined by quantifying GC-FID peak areas. The number of moles of
reactant consumed in any experiment was calculated from the mass of
reactant consumed and the molecular weight of the reactant. Selectivity is
defined here as the molar flow rate of product divided by molar flow rate of
reactant consumed. Yield is defined here as conversion times selectivity.
Initial conversion data were obtained by extrapolating the conversion
vs time-on-stream data to zero time on stream by using a linear fit. These
initial conversion data were used to find the fraction of anisole reactant
unconverted as a function of inverse WHSV, as well as yield as a function
of conversion and selectivity as a function of conversion.
Identification of Primary and Nonprimary Products. Selectivity vs.
conversion plots were used to determine which products were primary
and which were nonprimary, on the basis of the ordinate-intercepts of
the linear regression line through the data points; data that determine an
ordinate axis intercept of the regression line significantly different from
zero (with 95% confidence limits) are considered to be indicative of
primary products.43,44
Determination of Reaction Rates from Differential Conversion Data.
Data were plotted to demonstrate that some conversions were differential.
The pseudo-first-order rate constant for the overall disappearance of anisole
was determined from a semilogarithmic plot of fraction of reactant
unconverted, (1 X), as a function of inverse WHSV. The pseudo-first-
order rate constants for the production of primary products were deter-
mined from plots of conversion vs inverse space velocity.
dx.doi.org/10.1021/ef2010699 |Energy Fuels 2011, 25, 4776–4785
Energy & Fuels
Table 1. Overall Mass Balance Closure Dataa
experiment mass balance time on mass of liquid mass of liquid collected from
number closure (%) stream (min) fedb (g)
1 94.7 347 10.4
2 99.5 286 8.56
3 99.8 403 12.0
4 98.9 382 11.4
5 99.2 358 10.7
6 100.5 381 11.4
7 101.0 170 5.06
a
The data in each row represent results from an individual experiment. b The data showing liquid fed, liquid collected from condenser, and reactant
leaving the condenser in the vapor phase are cumulative values for the length of the experiment.
’ RESULTS
Catalyst Physical Properties. The BET surface area of the
catalyst was found to be 206 ( 1 m2/g, and the dispersion of the
platinum was found to be approximately 0.25.
Mass Balance Closures. Mass balance closures were typically
99.5 ( 1.0% (and they were generally greater than 95%) in
experiments with anisole conversions up to 17% (Table 1). The
reactant and most products have low vapor pressures at the exit
temperature of the condenser, and we, therefore, infer that they
were almost completely condensed. The mass of reactant leaving
the condenser in the vapor phase was determined to be between
2.5 and 2.8% of the mass fed into the reactor, and it is accounted
for in the mass balance calculation (Table 1). The contributions
of the products exiting the condenser in the vapor phase, which
generally have lower vapor pressures at the temperature of the
condenser, constitute a negligible contribution to the overall
mass balance. As a result, mass balance closures were not signi-
ficantly different from 100% even when a quantitative accounting
for products exiting the condenser in the gas phase was omitted.
The changes in mass of the packed bed were negligible relative to
other terms in the mass balance and did not contribute sig-
nificantly to the overall mass balance.
Major, Minor, and Trace Products of Anisole Conversion.
Dozens of products were identified in the conversion of anisole
catalyzed by Pt/Al2O3. Data were obtained at conversions as low
as 0.01 to determine primary reactions and the associated kinetics
parameters. Product formation data were also obtained at higher
conversions, up to X = 0.2, to identify nonprimary products. As a
control, experiments were performed using a bed of only α-
Al2O3 (without catalyst); essentially no conversion (X < 0.001)
was observed under these conditions.
The most abundant compounds identified at an anisole
conversion of approximately 0.2 are listed in Table 2. The major
products include methane, benzene, cyclohexanone, 2-methyl-
phenol, 2-methylanisole, phenol, and 2,6-dimethylphenol. The
conversions to these products were determined quantitatively.
Other products formed in relatively high yields include 4-methyl-
phenol, methoxycyclohexane, and 4-methylanisole. Water and
methanol were products observed by GC-MS but not quantified.
Trace products (identified only qualitatively) included methyl-
cyclohexanone, cyclohexane, methylcyclohexane, 1,1-dimethyl-
cyclohexane, o-xylene, p-xylene, 2,6-dimethylanisole, 2,4-dimethyl-
phenol, and trimethylphenol.
Conversion of Anisole as a Function of Time on Stream
and of Inverse Space Velocity. The conversion of anisole
catalyzed by Pt/Al2O3 as a function of time on stream at various
ARTICLE
mass of reactant leaving mass of liquid remaining in
condenserb (g) condenser as vaporb (g) condenser (g), estimated
9.04 0.26 0.5
7.62 0.20 0.5
11.2 0.34 0.5
10.5 0.32 0.5
9.81 0.30 0.5
10.7 0.32 0.5
4.47 0.14 0.5
space velocities is shown in Figure 2. These data demonstrate
catalyst deactivation. In a typical experiment, the deactivation
led to a decline in conversion of about 50% in 6 h. The yields
of various products vs time on stream do not suggest that
deactivation affects a particular reaction class more strongly
than the others. Initial conversions were determined by extra-
polating the data to zero time on stream. Error bars on the
data are shown for experiments carried out with a WHSV of
34 (g of reactant)/(g of catalyst  h). The data indicate that
higher space velocities lead to lower initial conversions, as
expected.
Development of a Quantitative Reaction Network. Plots of
selectivity (molar flow rate of product divided by molar flow rate
of reactant consumed) as a function of conversion were used to
identify which products were primary and which were not.43,44
Data for each product were fitted with a straight line and
extrapolated to zero conversion; intercepts of linear regression
lines significantly different from zero selectivity at zero conver-
sion (determined with 95% confidence limits) indicate primary
products. The selectivity-conversion data observed for anisole
(Figure 3) indicate that phenol, 2-methylphenol, 4-methyl-
phenol, 2-methylanisole, and 2,6-dimethylphenol were pri-
mary products and that benzene and cyclohexanone were
higher-order products. We infer, however, that 2,6-dimethyl
phenol was produced from anisole by a sequence of reactions
and, in small quantities, from feed impurities (<0.2%) such as
methylphenols.
The first step in the determination of a reaction network is to
infer the likely reaction classes from the identities of the products.
Thus, analysis of the products can give an indication of the reaction
classes in the conversion of anisole catalyzed by Pt/Al2O3.
The most abundant products point to the following important
(i.e., kinetically significant) reaction classes: hydrogenolysis (indi-
cated, for example, by the formation of phenol and methane),
hydrodeoxygenation (indicated, for example, by the formation of
benzene), hydrogenation (indicated, for example, by the formation
of cyclohexanone), and methyl group transfer (transalkylation)
(indicated, for example, by the formation of 2-methylphenol).
We infer that phenol is formed in both hydrogenolysis
and transalkylation reactions; other major products, including
2-methylanisole and 2-methylphenol, likely result from single
methyl group transfer reactions. 2,6-Dimethylphenol is inferred
to have been formed in sequential transalkylation reactions.
Methanol and benzene are inferred to have been formed by
hydrogenolysis of the C O bond, referred to here as hydro-
deoxygenation. Cyclohexanone is inferred to have been formed
by a sequence of reactions: removal of the methyl group bonded
4779 dx.doi.org/10.1021/ef2010699 |Energy Fuels 2011, 25, 4776–4785
Energy & Fuels ARTICLE

Table 2. Most Abundant Products and Trace Products Formed in the Conversiona of Anisole Catalyzed by Pt/Al2O3
(Compounds Identified in Liquid Product)b
classification based on
product abundance in product stream basis for identification of product basis for quantification of product

benzene major comparison of GC trace with that of standard sample FID calibration curve
methoxycyclohexane minor MS EI database n/a
cyclohexanone major comparison of GC trace with that of standard sample FID calibration curve
2-methylanisole major comparison of GC trace with that of standard sample FID calibration curve
4-methylanisole minor comparison of GC trace with that of standard sample n/a
phenol major comparison of GC trace with that of standard sample FID calibration curve
2-methylphenol major comparison of GC trace with that of standard sample FID calibration curve
4-methylphenol minor comparison of GC trace with that of standard sample n/a
2,6-dimethylphenol major comparison of GC trace with that of standard sample FID calibration curve
cyclohexane trace comparison of GC trace with that of standard sample n/a
methylcyclohexane trace MS EI database n/a
1,1 dimethylcyclohexane trace MS EI database n/a
p-xylene trace MS EI database n/a
o-xylene trace MS EI database n/a
2-methylcyclohexanone trace MS EI database n/a
2,6-dimethylanisole trace MS EI database n/a
2,4-dimethylphenol trace MS EI database n/a
trimethylphenol trace MS EI database n/a
water n/a MS EI database n/a
methanolc n/a MS EI database n/a
a
Conversion conditions: temperature, 573 K; WHSV, 4.46 (g of reactant)/(g of catalyst  h); initial conversion of anisole was approximately 0.2. The
retention times of the compounds identified in the liquid samples were consistent with the retention times of the compounds determined in experiments
with authentic calibration samples. b Compounds were identified with the NIST EI mass spectral database and by requiring that the Agilent quality
match factor (Qual) score be greater than 90; other isomers, for example, other dimethylanisole isomers, are possible. Some compounds were confirmed
by comparison with a GC trace characterizing standard samples. c Methanol was observed in liquid samples; its concentration in the gas phase was not
quantified.

The trace products are inferred to have been formed by

Figure 2. Change in anisole conversion during operation of a flow reactor
at 573 K and at various values of WHSV (WHSV in units of (g of reactant)/
(g of catalyst  h)): 18 (b), 34 ()), 150 (O), and 440 (9). An average of
duplicate values is shown for WHSV = 34 (g of reactant)/(g of catalyst  h).
to oxygen by hydrogenolysis or dealkylation and hydrogenation
of the aromatic ring.
Transalkylation reactions are inferred to have produced the
minor products 4-methylphenol and 4-methylanisole. Sequential
hydrogenation reactions of the aromatic ring are inferred to have
produced methoxycyclohexane.
4780
sequential reactions. These products can be accounted for by
the following reaction classes: transalkylation and hydrogenation
of the aromatic ring, leading to methylcyclohexanone, and hydro-
deoxygenation, hydrogenation, and transalkylation, accounting
for cyclohexane and methylcyclohexane. Multiple transalkylation
reactions account for methylphenols and methylanisoles with
multiple methyl substituents (e.g., various dimethylphenol iso-
mers and dimethylanisole isomers).
A partial statement of the reaction network, representing just
the primary products and other important products, is shown in
Figure 4. According to this representation, hydrogenolysis,
methyl group transfer, hydrodeoxygenation, and hydrogenation
are the kinetically significant reaction classes in the anisole con-
version catalyzed by Pt/Al2O3 in the presence of H2. Specifically,
methyl group transfer to methylphenols produced dimethylphe-
nols, which we infer eventually led to trimethylphenols and
tetramethylphenols. Methylbenzene (toluene) could be pro-
duced from either methylphenol or methylanisole by hydro-
deoxygenation reactions, which also lead to the formation of
benzene from phenol or anisole.
The data allow a quantitative characterization of the overall
conversion of anisole catalyzed by Pt/Al2O3. The overall anisole
conversion is well represented by first-order kinetics (Figure 5).
The pseudo-first-order rate constant for the disappearance of
anisole was found to be 19 L/(g of catalyst  h) under the
conditions stated in the caption of Figure 2. Using estimates of
dx.doi.org/10.1021/ef2010699 |Energy Fuels 2011, 25, 4776–4785
Energy & Fuels ARTICLE

Figure 3. Selectivity for the formation of several products in the conversion of anisole catalyzed by Pt/Al2O3 in the presence of H2 at 573 K; error bars
were determined in replicate experiments at conversions of approximately 0.07 and 0.16. Data for each product were fitted with a straight line and
extrapolated to zero conversion; intercepts of regression lines significantly different from zero selectivity at zero conversion (analyzed with 95%
confidence limits) indicate primary products. Primary products in this case are phenol (a), 2-methylphenol (b), 2-methylanisole (f), and 2,6-
dimethylphenol (d), and those with intercepts not significantly different from zero (determined with 95% confidence limits) are considered to be
evidence of higher-order products, in this case benzene (c) and cyclohexanone (e). The selectivity-conversion plot for 4-methylphenol (ESI Figure 1)
indicates that it is a primary product.

the diameter and density of catalyst particles, the average dia-
meter of the catalyst pores, and the reactant diffusivity, we judged
on the basis of the Weisz-Prater criterion, assuming spherical
particles and first-order kinetics, that influence of intraparticle
mass transport was negligible.
Data characterizing the formation of some of the products are
also well represented by first-order kinetics. The results (Figure 6)
allow the partially quantified statement of the reaction network
shown in Figure 4, which includes the pseudo-first-order rate
constants for each of the reactions, for example, the methyl group
transfer that results in the formation of 2-methylphenol from
anisole. The pseudo-first-order rate constants for the formation
of these products are summarized in Figure 4.
4781
The product that formed fastest from anisole was phenol. This
product was formed more than four times faster than 2-methyl-
phenol, and the other products were formed even more slowly.
The formation of 2-methylanisole was an order of magnitude
slower than the formation of 2-methylphenol. The formation of
4-methylphenol was nearly 2 orders of magnitude slower than
the formation of 2-methylphenol, which indicates a kinetic
preference for the substitution at the ortho position. Each of
the products is possibly formed by a single reaction; however,
these products could also be formed by sequences of reactions.
In contrast, we infer that 2,6-dimethylphenol was formed only in
a sequence of methyl-group transfers. The primary product, for
instance, can be inferred to be 2-methylphenol or 2-methylanisole.
dx.doi.org/10.1021/ef2010699 |Energy Fuels 2011, 25, 4776–4785
Energy & Fuels ARTICLE

Figure 4. Reaction network to primary products and to other important products based on analysis of selectivity-conversion plots for the conversion of
anisole and H2 catalyzed by Pt/Al2O3 at 573 K. H2, as a reactant, is omitted for simplicity. 2,6-Dimethylphenol appears (on the basis of the selectivity-
conversion plot) to be a primary product, but we infer that it must have been formed by a sequence of reactions. Pseudo-first-order rate constants for
the individual primary products formed in the conversion of anisole catalyzed by Pt/Al2O3 are in units of L/(g of catalyst  h). The reaction temperature
was 573 K. These rate constants were determined from the conversions to the individual products, which, for example, in the case of phenol, may be
formed in more than one reaction pathway, as shown here.

determined to be k = 0.86 L/(g of catalyst  h), and that found

Figure 5. Demonstration of first-order kinetics of overall conversion
of anisole catalyzed by Pt/Al2O3 under the conditions stated in the text.
Error bars of replicates are shown at inverse WHSV = 0.056 and 0.029
(g of catalyst  h)/(g of anisole).
The formation of benzene and of cyclohexanone, although
they are evidently not primary products, is in each case adequately
represented by first-order kinetics (Figure 7). The pseudo-
first-order rate constant characterizing benzene formation was
4782
for cyclohexanone formation was k = 0.53 L/(g of catalyst  h).
Presuming that methyl group transfer, hydrodeoxygenation,
hydrogenolysis, and hydrogenation are the important reaction
classes and by recognizing which compounds were primary
products and which were not, we inferred the more extensive
reaction network of Figure 8. As this network shows, most of the
products in the conversion of anisole were likely formed in
sequential reactions; they were not primary products. However, the
data are not sufficient to fully elucidate the nonprimary products.
The data are not sufficient to identify all of the primary
reactions. For example, phenol could have been formed as a
primary product via several pathways, each with a different
coproduct: methane, 2-methylanisole, and 4-methylanisole. Be-
cause the selectivity for formation of neither 2-methylanisole nor
4-methylanisole matches that of phenol, we infer that the primary
pathway for phenol formation is hydrogenolysis of anisole (to
give phenol and methane).
2-Methylphenol, as well as 4-methylphenol, can also be formed
via multiple pathways: intramolecular transalkylation of anisole
or intermolecular transalkylation involving phenol and anisole.
The further addition of methyl substituents to the aromatic ring
to produce dimethylphenols, trimethylphenols, and so forth
allows for a number of possible pathways. 2-Methylanisole and
4-methylanisole are inferred to be formed primarily from single
methyl group transfer reactions.
dx.doi.org/10.1021/ef2010699 |Energy Fuels 2011, 25, 4776–4785
Energy & Fuels
Figure 6. Semilogarithmic plots of the conversion of anisole in the presence of H2 to give phenol (O), 2-methylphenol (b), 2,6-dimethylphenol (0),
2-methylanisole (9), and 4-methylphenol (1) at 573 K. The term (1 Xi) represents the conversion to product i. Conversion was varied by changing
the catalyst mass in the packed bed.
Figure 7. Semilogarithmic plots of the conversion of anisole in the
presence of H2 to give cyclohexanone (O) and benzene (b) at 573 K.
The term (1 Xi) represents the conversion of anisole to product i.
Conversion was varied by changing the catalyst mass in the packed bed.
Benzene was also possibly formed via parallel pathways, both
involving hydrodeoxygenation. From the (qualitative) observa-
tion of methanol, we infer that hydrodeoxygenation of anisole
produces methanol and benzene. Hydrodeoxygenation of phe-
nol can also produce benzene and water. Hydrogenation of
phenol has been shown to produce cyclohexanone.45,46 These
reactions with hydrogen likely occurred with methyl-substituted
phenols and anisoles to form methyl-substituted benzenes.
In summary, the reaction network of Figure 8 accounts for our
data and accounts for the kinetically important reaction classes,
but we recognize that it is an approximation that could be
improved with the availability of more extensive data.
’ DISCUSSION
The catalytic conversion of anisole catalyzed by platinum
supported on γ-Al2O3, an acidic support, shows some similarity
to anisole conversion catalyzed by solid acids without noble
metals. For example, Chantal et al.,32 using HZSM-5 as a catalyst,
observed high yields of phenol, methylphenols, and dimethyl-
phenols at 623 K with a residence time in a plug-flow reactor of
0.83 h. Using HZSM-5 as a catalyst, Zhu et al.35 observed the
formation of phenol, methylphenols, and methylanisoles in high
yields at 673 K and over a range of residence times in a plug-flow
4783
ARTICLE
reactor ranging from less than 0.05 to 1.0 h. For comparison, our
residence times ranged from 2.3  10 3 to 56.7  10 3 h.
In their experiments with acidic catalysts, Chantal et al.32 and
Zhu et al.35 also observed the removal of oxygen from anisole and
the formation of aromatic products. The highest selectivity to
aromatics indicated by their data was 0.05,32 which is lower than
our observed selectivity to benzene of almost 0.10. Chantal
et al.32 and Zhu et al.35 used higher temperatures and higher
average residence times than ours, and we suggest that the
differences in severity between their conditions and ours account
in part for the different product distributions, but we attribute the
differences primarily to the presence of the noble metal in our
catalyst and the lack of such a metal in theirs.
In experiments with a bifunctional hydrotreating catalyst,
sulfided Ni Mo/SiO2 Al2O3, which contains an acidic sup-
port, Bredenberg et al.37 also observed the formation of methyl-
phenols and methylanisole in the conversion of anisole at 573 K.
They also reported a selectivity for benzene formation of 0.055 at
an anisole conversion of 0.76. The data cannot be directly
compared with ours, which are characterized by a maximum
observed selectivity for benzene formation of 0.10, because the
conversions are dramatically different. The conversion and yield
data reported by Hurff and Klein38 indicate a selectivity for
benzene formation at high conversion similar to that of Breden-
berg et al.,37 although a precise value cannot be estimated at low
conversions because of the scale of the plot in the publication.38
Thus, the routes by which oxygen was removed from anisole in
the reported acid-catalyzed reactions are not clear from the
information presented by the authors. We emphasize that in
our case we attribute the oxygen removal largely to the role of
platinum in activating H2 for hydrodeoxygenation reactions.
There are numerous examples of similar reactions catalyzed by
noble metals, exemplified the hydrodeoxygenation of guaiacol
catalyzed by rhodium, palladium, and platinum supported on
zirconia.47 Ours is evidently the first report of the hydrode-
oxygenation of anisole catalyzed by a supported noble metal.
Hydroprocessing catalysts incorporating metals such as mo-
lybdenum have also been used for hydrodeoxygenation. For
example, Hurff and Klein38 and Bredenberg et al.37 used sulfided
CoMo/γ-Al2O3 for removal of oxygen from anisole, observing
benzene as a major product at high conversions in a batch
reactor; the benzene was evidently formed from phenol, which
was a major primary product according to their reaction network.
dx.doi.org/10.1021/ef2010699 |Energy Fuels 2011, 25, 4776–4785
Energy & Fuels
Figure 8. Reaction network for the conversion of anisole and H2 catalyzed by Pt/Al2O3 at 573 K. Hydrodeoxygenation, hydrogenolysis, and
hydrogenation reactions are represented by dashed arrows, and methyl group transfer reactions are represented by solid arrows.
In contrast, our results show the catalytic formation of benzene at
relatively low conversions of anisole, consistent with the catalytic
role of the platinum.
’ CONCLUSIONS
In comparison with the work of earlier investigators who
considered catalytic anisole conversion, we have been able to
develop a more extensive reaction network, including quanti-
fication of rates of formation of primary products. The data
enable us to infer relative contributions of the various reaction
classes. We infer the platinum catalyzed hydrogenolysis of the
anisole to produce methane and phenol, which is a kinetically
significant reaction under our conditions. All other primary
products were apparently produced by methyl group transfer
reactions. Higher-order products that were observed in rela-
tively high yields include benzene, formed by hydrodeoxygena-
tion of anisole or phenol, and cyclohexanone, formed by
hydrogenation of phenol. We infer that reactions in both of
these classes were catalyzed by the platinum. Methyl group
transfer apparently catalyzed the formation of numerous higher-
order products such as dimethylanisoles, trimethylphenols, and
pentamethylbenzenes, formed, for example, from methylanisole
and anisole, dimethylphenol and anisole, and tetramethylbenzene
and anisole, respectively.
4784
ARTICLE
Although the reaction network could be elucidated in more
detail than we have presented, with the benefit of additional data
(such as could be obtained with intermediates in the feed
stream), an important practical inference that is already clear
on the basis of our results is that selective oxygen removal from
compounds such as anisole may require both (a) catalysts with
functions that are active for hydrodeoxygenation (such as noble
metals) and (b) substantially higher H2 partial pressures than we
have investigated in this work.
’ ASSOCIATED CONTENT
bS Supporting Information. Table containing the composi-
tion of the gas calibration standard and a figure showing 4-methyl-
phenol selectivity-conversion data. This material is available free of
charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: bcgates@ucdavis.edu.
Present Addresses
§
Argonne National Laboratory, Chemical Sciences and Engi-
neering Division, 9700 South Cass Ave, CSE/205, Chicago, IL
60439, USA.
dx.doi.org/10.1021/ef2010699 |Energy Fuels 2011, 25, 4776–4785
Energy & Fuels ARTICLE

’ ACKNOWLEDGMENT (31) Kallury, R. K. M. R.; Restivo, W. M.; Tidwell, T. T.; Boocock,

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